JPS62260808A - O-substituted phenylacetylene polymer - Google Patents
O-substituted phenylacetylene polymerInfo
- Publication number
- JPS62260808A JPS62260808A JP10365686A JP10365686A JPS62260808A JP S62260808 A JPS62260808 A JP S62260808A JP 10365686 A JP10365686 A JP 10365686A JP 10365686 A JP10365686 A JP 10365686A JP S62260808 A JPS62260808 A JP S62260808A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- alkyl
- formula
- alkyl group
- substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 25
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical class C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 title claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000004665 trialkylsilyl group Chemical group 0.000 claims abstract description 5
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 2
- -1 resists Substances 0.000 abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 4
- 125000005842 heteroatom Chemical group 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 239000003505 polymerization initiator Substances 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- VBEPMNWLWNKUGJ-UHFFFAOYSA-N 2-ethynyl-1,3,5-trimethylbenzene Chemical group CC1=CC(C)=C(C#C)C(C)=C1 VBEPMNWLWNKUGJ-UHFFFAOYSA-N 0.000 description 1
- PPWNCLVNXGCGAF-UHFFFAOYSA-N 3,3-dimethylbut-1-yne Chemical group CC(C)(C)C#C PPWNCLVNXGCGAF-UHFFFAOYSA-N 0.000 description 1
- UMVNNFICWDBWPL-UHFFFAOYSA-N 3-ethynyl-1,2,4,5-tetramethylbenzene Chemical group CC1=CC(C)=C(C)C(C#C)=C1C UMVNNFICWDBWPL-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910009045 WCl2 Inorganic materials 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QCQALVMFTWRCFI-UHFFFAOYSA-N oct-2-yne Chemical compound CCCCCC#CC QCQALVMFTWRCFI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- GHUURDQYRGVEHX-UHFFFAOYSA-N prop-1-ynylbenzene Chemical group CC#CC1=CC=CC=C1 GHUURDQYRGVEHX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- DCGLONGLPGISNX-UHFFFAOYSA-N trimethyl(prop-1-ynyl)silane Chemical compound CC#C[Si](C)(C)C DCGLONGLPGISNX-UHFFFAOYSA-N 0.000 description 1
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、従来存在しなかった重合体に係り、更に詳し
くは、オルト位に置換基を有するフェニルアセチレン類
を単量体とする新規な重量平均分子量１万以上の高重合
度の重合体（単独重合体及び／又は共重合体）に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polymer that has not existed heretofore, and more specifically, to a novel polymer whose monomer is a phenylacetylene having a substituent at the ortho position. It relates to a high polymerization degree polymer (homopolymer and/or copolymer) having a weight average molecular weight of 10,000 or more.
（従来の技術）
本発明者らはさきに、六・・ロゲン化タングステンや五
ノ・ロゲン化モリブデンを主体とする触媒を用いて１−
アルキルアセチレン類の重合を行った。アルキル基がか
さ高いほど高分子量のポリマーが得られ、ｔ−ブチル基
のようなかさ高い置換基をもつ化合物から得られるポリ
マーは、膜形成能を有し、酸素富化膜として有望である
ことが分かった。(Prior art) The present inventors have previously discovered that 1-
Polymerization of alkyl acetylenes was carried out. The bulkier the alkyl group, the higher the molecular weight of the polymer obtained, and polymers obtained from compounds with bulky substituents such as t-butyl groups have membrane-forming ability and are promising as oxygen-enriching membranes. Do you get it.
（発明が解決しようとする問題点）
しかしながら、１−フェニルアセチレンやｌ−ナフチル
アセチレンは、重合はするが、さほどの高分子量体は得
られず、膜形成能を有するものは得られていない、とい
う間頂点がちった５゜本発明は、１−フェニルアセチレ
ンのフェニル基のオルト位に置換式を導入することてよ
り、上記の従来の問題点を解決しうる新規なオルト置換
フェニルアセチレン類の高重合度の重合体の提供を目的
とする。(Problems to be Solved by the Invention) However, although 1-phenylacetylene and l-naphthylacetylene can be polymerized, it is not possible to obtain a material with a high molecular weight, and no material having film-forming ability has been obtained. The present invention provides novel ortho-substituted phenylacetylenes that can solve the above conventional problems by introducing a substituent at the ortho position of the phenyl group of 1-phenylacetylene. The purpose is to provide a polymer with a high degree of polymerization.
（問題点を解決するだめの手段）
本発明者らは、かかる目的を達成すべく鋭意研究を進め
た結果、本発明に到達した。すなわち、本発明は、一般
式ＣＩ）及びＣＩ）（式中Ｒ１は炭素数１〜８のアルキ
ル基を示し、Ｘは水素原子又は炭素数１〜８のアルキル
基を示し、ｌはθ〜４の整数を示し、Ｒ２は水素原子又
は塩素原子を示しＲ３はアルキル基、アリール基又はト
リアルキルシリル基を示し、またｍは２以上の整数を示
し、ｎはＯ又は自然数を示す。）からなる構造式で表わ
される重量平均分子量１万以上のオルト位に置換基を有
するフェニルアセチレン重合体を要旨とするものである
。(Means for Solving the Problems) The present inventors have conducted intensive research to achieve the above object, and as a result, have arrived at the present invention. That is, the present invention provides general formulas CI) and CI) (where R1 represents an alkyl group having 1 to 8 carbon atoms, X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and l represents θ~4 , R2 represents a hydrogen atom or a chlorine atom, R3 represents an alkyl group, aryl group, or trialkylsilyl group, m represents an integer of 2 or more, and n represents O or a natural number). The gist is a phenylacetylene polymer having a substituent at the ortho position and having a weight average molecular weight of 10,000 or more as represented by the structural formula.
本発明における主成分に用いられる原料モノマーである
オルト位に置換基を有するフェニルアセチレン類は、下
記一般式ＣＩ）
（式中Ｒ１は炭素数１〜８のアルキル基を示し、該アル
キル基の水素原子の１個以上かへテロ基で置換されてい
てもよく、Ｘは水素原子又は炭素数１〜８のアルキル基
を示し、ｅはＯ〜４の整数を示す。）で表わされる化合
物である。そしてこれらの化合物の具体例としては、オ
ルトメチルフェニルアセチレン、オルトエチルフェニル
アセチレン、オル） −ｔ −ブチルフェニルアセチレ
ン、オルト−ｎ−オクチルフェニルアセチレン、メシチ
ルアセチレン、２，４．６−１−リメチルフェニルアセ
チレン、２，３，４．５−テトラメチルフェニルアセチ
レン、２，３，５．６−テトラメチルフェニルアセチレ
ン等を挙げることができる。The phenylacetylenes having a substituent at the ortho position, which are the raw material monomers used as the main component in the present invention, have the following general formula CI) (wherein R1 represents an alkyl group having 1 to 8 carbon atoms, and the hydrogen of the alkyl group is One or more atoms may be substituted with a hetero group, X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and e represents an integer of 0 to 4.) . Specific examples of these compounds include orthomethylphenylacetylene, orthoethylphenylacetylene, ortho-t-butylphenylacetylene, ortho-n-octylphenylacetylene, mesitylacetylene, 2,4.6-1-ly Examples include methylphenylacetylene, 2,3,4.5-tetramethylphenylacetylene, and 2,3,5.6-tetramethylphenylacetylene.
共重合体の場合、他の成分に用いられるモノマーとして
は、一般式ＣＩＶ）
Ｒ２−Ｃ三Ｃ−Ｒ３・・・・・・・・・ ＣＩＶ）で表
わされる化合物が用いられる。ここにＲ２は水素原子、
アルキル基又は塩素原ギを示し、Ｒ３はアルキル基、ア
リール基又はトリアルキルシリル基を示す。このアルキ
ル
数が１〜１２のアルキル基であり、直鎖状であっても分
岐状であってもよく、さらにヘテロ基で置換されていて
もよい。アリール基はｇＴｈ で表わされ、Ｙはアル
キル基、アリール基、アラルキル基、アルコキ・ン基、
アラルキル基、ニトロ基、アミン基などの置換基を示し
、ｋはＯ〜５の整数を示す。又、トリアルキルシリル基
はＳｉＲ′Ｒ″Ｒ′／ｌで表わされ、Ｒ′、Ｒ“、Ｒ″
′ は同一でも異なっていてもよく、いずれもアルキ
ル基を示す。かかる具体的な化合物としては、ｔ−ブチ
ルアセチレン、フェニルアセチレン、１−クロロ−２−
フェニルアセチレン、２−オクチン、２−デ゛ンン，ト
リメチルシリルアセチレン、トリメチルシリルプロピン
等が挙げられる。In the case of a copolymer, the monomer used for the other components is a compound represented by the general formula CIV) R2-C3C-R3...CIV). Here R2 is a hydrogen atom,
It represents an alkyl group or a chlorine atom, and R3 represents an alkyl group, an aryl group, or a trialkylsilyl group. This is an alkyl group having 1 to 12 alkyl numbers, which may be linear or branched, and may be further substituted with a hetero group. The aryl group is represented by gTh, and Y is an alkyl group, an aryl group, an aralkyl group, an alkoxy group,
It represents a substituent such as an aralkyl group, a nitro group, or an amine group, and k represents an integer of O to 5. Further, the trialkylsilyl group is represented by SiR'R"R'/l, and R', R", R"
′ may be the same or different, and both represent an alkyl group. Specific examples of such compounds include t-butylacetylene, phenylacetylene, 1-chloro-2-
Examples include phenylacetylene, 2-octyne, 2-dyne, trimethylsilylacetylene, trimethylsilylpropyne, and the like.
本発明のオルト位に置換基を有するフェニルアセチレン
の重合体を製造する方法としては、例えば次の方法が挙
げられる。Examples of the method for producing the phenylacetylene polymer having a substituent at the ortho position of the present invention include the following method.
重合開始剤としては、遷移金属のＭｏ， Ｗ， Ｎｂ。As a polymerization initiator, transition metals such as Mo, W, and Nb are used.
Ｔａ等を使用できるが、とくにＭｏ，Ｗ化合物の使用が
望ましく、かかる方法としては次の三つが挙げられる。Although Ta and the like can be used, it is particularly desirable to use Mo and W compounds, and the following three methods can be mentioned as such methods.
（イ） Ｍ ｏ Ｃ Ｊ ｓ ＋ Ｍｏ Ｂ ｒ ｓ
、 Ｗ Ｃ ７１ａ 等のハロゲン化モリブデ／，ハロ
ゲン化タングステンを使用する方法。(a) Mo C J s + Mo B r s
A method using molybdenum halide/tungsten halide such as WC 71a.
（口）ハロゲン化モリブデン、ハロゲン化タングステン
を主触媒とし還元剤を第二成分とする開始剤を使用する
方法。この場合、主成分の・・ロゲン化モリブデンとし
てはＭｏＣＪ，、が好ましく、ハロゲン化タングステン
としてはＷＣｌ２が好ましい。第二成分の還元剤には有
機金属化合物が用いられ、アルミニウム、ホウ素，ケイ
素，スズ、アンチモン、ビスマス、リチウム等を含むも
のが挙げられる。(1) A method using an initiator containing molybdenum halide or tungsten halide as the main catalyst and a reducing agent as the second component. In this case, the molybdenum halide as the main component is preferably MoCJ, and the tungsten halide is preferably WCl2. An organic metal compound is used as the second component reducing agent, and examples thereof include those containing aluminum, boron, silicon, tin, antimony, bismuth, lithium, and the like.
（ハ） ％開昭５７−３６１０６号公報記載の方法で用
いた開始剤、すなわち、Ｍｏ （Ｃｏ）６− ＣＣｌ４
−ｈν、ｗ（ｃｏ）６−ｃｃｇ４−ｈνを用いる方法。(c) % Initiator used in the method described in Japanese Patent Publication No. 57-36106, that is, Mo (Co)6-CCl4
-hν, a method using w(co)6-ccg4-hν.
上記（イ）及び（ロ）の方法における重合主触媒の使用
量は、通常、モノマーに対して０．１〜５モル係が適当
である。また、上記（ロ）の方法における還元剤の使用
量は、還元剤対主触媒のモル比で０、３〜３の範囲が好
ましい。The amount of the polymerization main catalyst used in the above methods (a) and (b) is usually 0.1 to 5 moles relative to the monomer. Further, the amount of the reducing agent used in the method (b) above is preferably in the range of 0.3 to 3 in molar ratio of reducing agent to main catalyst.
これらの方法の重合反応は溶媒中で行うのがよく、かか
る溶媒としてはトルエンなどの芳香族炭化水素、シクロ
ヘキサンなどの脂肪族炭化水素、四塩化炭素、二塩化エ
チレン等のハロゲン化炭化水素、アニソール、ジブチル
エーテル、ジオキサン等のエーテル、アセト／、アセト
フェノンなどのケト／、酢酸エチルなどのエステルなど
が挙げられる。The polymerization reaction in these methods is preferably carried out in a solvent, and such solvents include aromatic hydrocarbons such as toluene, aliphatic hydrocarbons such as cyclohexane, halogenated hydrocarbons such as carbon tetrachloride and ethylene dichloride, and anisole. , dibutyl ether, ethers such as dioxane, aceto/, keto/ such as acetophenone, and esters such as ethyl acetate.
重合反応温度は一３０〜＋１００℃の範囲が好ましく、
特に０〜７０°Ｃが好ましい。The polymerization reaction temperature is preferably in the range of -30 to +100°C,
Particularly preferred is 0 to 70°C.
重合時間は０．５〜２４時間が好ましい。また、重合は
乾燥窒素雰囲気下で行うのがよい。The polymerization time is preferably 0.5 to 24 hours. Further, the polymerization is preferably carried out under a dry nitrogen atmosphere.
共重合を行う場合、主成分に用いられるオルト置換フェ
ニルアセチレン類と他の成分に用いられる置換アセチレ
ン類との比は、どのような比率であってもよい。When performing copolymerization, the ratio of ortho-substituted phenylacetylenes used as the main component to substituted acetylenes used as other components may be any ratio.
かくして製造される本発明の新規な重合体は、重量平均
分子量（光散乱法による）１万以上の高重合度の重合体
である。しかも、これらの生成重合体は、側鎖として置
換基が存在するため、ポリアセチレンとは異なり、空気
に対し安定であり、かさ高い置換基の存在により耐熱材
料として期待できる。また、ハロゲン化炭化水素、エー
テル、ケトン等の有機溶媒に可溶性であって、多くは優
れた膜形成能を有する。更には、共役二重結合の存在に
より、半導体材料、レジスト材料等にも利用可能である
。The novel polymer of the present invention produced in this way has a high degree of polymerization with a weight average molecular weight (as measured by a light scattering method) of 10,000 or more. Furthermore, since these produced polymers have substituents as side chains, they are stable in air, unlike polyacetylene, and can be expected to be heat-resistant materials due to the presence of bulky substituents. In addition, they are soluble in organic solvents such as halogenated hydrocarbons, ethers, and ketones, and many have excellent film-forming ability. Furthermore, due to the presence of conjugated double bonds, it can also be used in semiconductor materials, resist materials, etc.
（実施例）
次に、本発明を実施例により更に具体的に説明するが、
本発明はこれらの実施例に限定されるものではない。(Example) Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.
なお、下記の実施例において、分子量は重量平均分子量
（Ｍｗ ）であり、光散乱法により求めたものである。In addition, in the following examples, the molecular weight is a weight average molecular weight (Mw), which was determined by a light scattering method.
又、「慢」は、とくに断らない限り、「重量係」である
。Also, ``arrogant'' refers to ``weight'' unless otherwise specified.
実施例１
充分に精製したトルエン１！中に、乾燥窒素雰囲気下、
よく攪拌しなから五塩化モリブデン２０ミリモルとテト
ラ−ｎ−ブチルスズ２０ミリモルを加え３０°Ｃで溶解
した。この溶液に１、０モルのオルトメチルフェニルア
セチレンを添加し、３０℃で重合を進行させた。２４時
間後、反応混合物を大量のメタノール中に投入して生成
重合体を沈殿させ、炉別、乾燥した。重合体の収率は９
０係であり、その分子量は２０万であった。Example 1 Thoroughly purified toluene 1! Under a dry nitrogen atmosphere,
While stirring well, 20 mmol of molybdenum pentachloride and 20 mmol of tetra-n-butyltin were added and dissolved at 30°C. 1.0 mol of orthomethylphenylacetylene was added to this solution, and polymerization was allowed to proceed at 30°C. After 24 hours, the reaction mixture was poured into a large amount of methanol to precipitate the produced polymer, which was then separated in an oven and dried. The yield of polymer is 9
0, and its molecular weight was 200,000.
得られた重合体は、赤褐色粉末であり、ジクロルエタン
等の・・ロゲン化炭化水素、テトラヒドロフラン等のエ
ーテル、アセトフェノン等のケトンなどの有機溶媒に可
溶であった。The obtained polymer was a reddish brown powder and was soluble in organic solvents such as rogenated hydrocarbons such as dichloroethane, ethers such as tetrahydrofuran, and ketones such as acetophenone.
生成重合体のスペクトルデーターを添付図面の第１図（
ＩＲ）及び第２図（１３ＣＮＭＲ）に示す。The spectral data of the produced polymer is shown in Figure 1 of the attached drawings (
IR) and Figure 2 (13CNMR).
実施例２
実施例１の五塩化モリブデンとテトラ−ｎ −ブチルス
ズの代わりに六塩化タングステンを用いた以外は、実施
例１と同様に行ったところ、収率は８６係で分子量４１
万の赤褐色粉末の重合体が得られた。Example 2 The same procedure as in Example 1 was carried out except that tungsten hexachloride was used in place of molybdenum pentachloride and tetra-n-butyltin in Example 1. The yield was 86% and the molecular weight was 41.
A reddish-brown powder of 1,000 ml of polymer was obtained.
実施例３
開始剤としてタングステンカルボニルを用い、溶媒に四
塩化炭素を用いて、光を照射しながら２４時間重合反応
を行ったところ、収率は１００チで分子量１０７万の赤
褐色粉末が得られた。Example 3 Using tungsten carbonyl as an initiator and carbon tetrachloride as a solvent, a polymerization reaction was carried out for 24 hours while irradiating light, and a reddish brown powder with a yield of 100 cm and a molecular weight of 1,070,000 was obtained. .
実施例４
モノマーとしてオルトメチルフェニルアセチレン０．７
モルとフェニルアセチレン０．３モルを用いた以外は、
実施例１と同様にして重合を行ったところ、重合体の収
率は８０％であり、その分子量は１５万であった。Example 4 Orthomethylphenylacetylene 0.7 as monomer
mol and 0.3 mol of phenylacetylene were used.
Polymerization was carried out in the same manner as in Example 1, and the yield of the polymer was 80%, and its molecular weight was 150,000.
実施例５
実施例１の重合温度を０℃にした以外は、実施例１と同
様にして重合を行ったところ、収率１００係で分子量２
６万の赤褐色ポリマーが得られた。Example 5 Polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature in Example 1 was changed to 0°C. The yield was 100% and the molecular weight was 2.
60,000 reddish-brown polymer was obtained.
実施例６
実施例１でトルエン溶媒の代わりに１．４−ジオキサン
を用いた以外は、実施例１と同様にして重合を行ったと
ころ、収率１００％で分子量２３万のポリマーが得られ
た。Example 6 Polymerization was carried out in the same manner as in Example 1 except that 1,4-dioxane was used instead of the toluene solvent in Example 1, and a polymer with a molecular weight of 230,000 was obtained with a yield of 100%. .
（発明の効果）
以上の結果から明らかなように、本発明のオルト位に置
換基を有するフェニルアセチレン重合体は、重量平均分
子量が１万以上、その多くは１０万以上の高重合度を示
す全く新規な高重合体であるばかりでなく、従来のポリ
アセチレンとは異なり空気に対し安定であり、ジクロル
エタンのようなハロゲン化炭化水素、テトラヒドロフラ
ン、ジオキサン、アニソール等のエーテル、アセトフェ
ノンのようなケトン等に可溶で、かつその多くは優れた
膜形成能を有する、などという工業的価値ある顕著な効
果を奏ゝるものである。したがって、分離漢、吸着材、
レジスト材、半導体材料、記憶材料等への応用が可能で
ある。(Effect of the invention) As is clear from the above results, the phenylacetylene polymer having a substituent at the ortho position of the present invention has a weight average molecular weight of 10,000 or more, and most of them exhibit a high degree of polymerization of 100,000 or more. Not only is it a completely new high polymer, but unlike conventional polyacetylene, it is stable against air, and is compatible with halogenated hydrocarbons such as dichloroethane, ethers such as tetrahydrofuran, dioxane, and anisole, and ketones such as acetophenone. They are soluble, and most of them have excellent film-forming properties, which have remarkable effects of industrial value. Therefore, the separator, adsorbent,
It can be applied to resist materials, semiconductor materials, memory materials, etc.
第１図及び第２図は実施例１で得られた本発明の重合体
の一例のＩＲ及び１３ＣＮＩＶＩＲスペクトルを示す図
である。1 and 2 are diagrams showing IR and 13CNIVIR spectra of an example of the polymer of the present invention obtained in Example 1.
Claims (1)
式、化学式、表等があります▼・・・〔II〕 （式中、Ｒ＾１は炭素数１〜８のアルキル基を示し、Ｘ
は水素原子又は炭素数１〜８のアルキル基を示し、ｌは
０〜４の整数を示し、Ｒ＾２は水素原子又は塩素原子を
示し、Ｒ＾３はアルキル基、アリール基又はトリアルキ
ルシリル基を示し、またｍは２以上の整数を示し、ｎは
０又は自然数を示す。）からなる構造式で表わされる重
量平均分子量１万以上のオルト位に置換基を有するフェ
ニルアセチレン重合体。(1) General formulas [I] and [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I]▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] (In the formula, R^ 1 represents an alkyl group having 1 to 8 carbon atoms;
represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, l represents an integer of 0 to 4, R^2 represents a hydrogen atom or a chlorine atom, and R^3 represents an alkyl group, an aryl group, or a trialkylsilyl group. m represents an integer of 2 or more, and n represents 0 or a natural number. ) A phenylacetylene polymer having a substituent at the ortho position and having a weight average molecular weight of 10,000 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10365686A JPH0617414B2 (en) | 1986-05-06 | 1986-05-06 | Phenylacetylene polymer having a substituent at the ortho position |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10365686A JPH0617414B2 (en) | 1986-05-06 | 1986-05-06 | Phenylacetylene polymer having a substituent at the ortho position |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62260808A true JPS62260808A (en) | 1987-11-13 |
| JPH0617414B2 JPH0617414B2 (en) | 1994-03-09 |
Family
ID=14359822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10365686A Expired - Lifetime JPH0617414B2 (en) | 1986-05-06 | 1986-05-06 | Phenylacetylene polymer having a substituent at the ortho position |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0617414B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1000434C2 (en) * | 1994-05-24 | 1995-11-24 | Bend Research | Acetylene copolymers and membranes thereof. |
| JP2005319389A (en) * | 2004-05-07 | 2005-11-17 | Hokkaido Univ | Molecule adsorbing material, manufacturing method therefor and gas storage apparatus |
| JP2008127438A (en) * | 2006-11-17 | 2008-06-05 | Canon Inc | Manufacturing method of substituted polyacetylene film |
| WO2009028728A1 (en) * | 2007-08-31 | 2009-03-05 | Canon Kabushiki Kaisha | Block polymer and device |
| JP2011195390A (en) * | 2010-03-19 | 2011-10-06 | Kuraray Co Ltd | Hydrogen adsorption material, storage material, and method for storing hydrogen |
-
1986
- 1986-05-06 JP JP10365686A patent/JPH0617414B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1000434C2 (en) * | 1994-05-24 | 1995-11-24 | Bend Research | Acetylene copolymers and membranes thereof. |
| JP2005319389A (en) * | 2004-05-07 | 2005-11-17 | Hokkaido Univ | Molecule adsorbing material, manufacturing method therefor and gas storage apparatus |
| JP2008127438A (en) * | 2006-11-17 | 2008-06-05 | Canon Inc | Manufacturing method of substituted polyacetylene film |
| WO2009028728A1 (en) * | 2007-08-31 | 2009-03-05 | Canon Kabushiki Kaisha | Block polymer and device |
| US7786235B2 (en) | 2007-08-31 | 2010-08-31 | Canon Kabushiki Kaisha | Block polymer and device |
| US8349978B2 (en) | 2007-08-31 | 2013-01-08 | Canon Kabushiki Kaisha | Block polymer and device |
| JP2011195390A (en) * | 2010-03-19 | 2011-10-06 | Kuraray Co Ltd | Hydrogen adsorption material, storage material, and method for storing hydrogen |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0617414B2 (en) | 1994-03-09 |
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